Monazo dyes containing two hydroxynaphthalene nuclei



Patented Dec. 30, 1924.

FRITZ STRAUB, OF BASEL, AND HERMANN SCHNEIDER, OF RIEHEN, NEAR BASKET, SWITZERLAND, ASSIGNOR-S T0 SOCIETY OF CHEMICAL INDUSTRY IN BASLE, 0F

BASEL, SWITZERLAND.

MONAZO DYES CONTAINING TWO HYDROXYNAPHTHALENE NUCLEI.

No Drawing.

To all whom it may concern) Be it known that we, FRITZ STRAUB, residing at Basel, Switzerland, and HERMANN SCHNEIDER-,residing at Riehen, near Basel, Switzerland, both citizens of the Confederation of Switzerland, have invented new and useful Improvements in Monazo Dyes Containing Two Hydroxynaphthalene Nuclei, of which the following/is a full, clear, and exact specification.

The present invention relates to new dyestuffs which constitute valuable dyestuffs capable of being after-chromed. The invention comprises the new dyestuifs, the method of their manufacture, as well as the fibres which have been dyed with'the new dyestufls.

It has been found that the dyestuffs pro duced by coupling the nitrated diazo-compound of l-amino-2-hydroxynaphthalene-4- sulphonic acid with a naphthol can be converted by treatment-with reducing agents into new black mordant dyeing dyestufl's presumably having the general formula:

(in which R indicates an hydroxynaphthalene nucleus to which the azo-bridge is at tached in an ortho-position to the hydroxyloup Y They form blackish-brown powders whlch dissolve in a sodium carbonate solution with Application filed March 31, 1924. Serial No. 703,250.

earth metals come chiefly into consideration, while other similarly acting agents, such as for instance ferrous hydroxide or carbonate may be mentioned. As a technical process there isbest used for the reduction such agents and methods as can be used after the coupling operation without any further procedure, such as the separation of the dyestufi' or the separation 'of metals as a se-. quence to the reduction.

The following examples illustrate the invention. the parts being by weight Example 1.

A suspension as concentrated as possible of the dyestufi' obtained by coupling 46.5 parts of a-nanhthol with 95 parts of the sodium salt of the nitrated diazo-compound of 1-amino-2-hydroxynaphthalenei-sulphonic acid, is added, while stirring, to a moltenmixture of 20 parts of water and 120 parts of crystallized sodium sulphide and the stirring of the mixture is continued for some time at the ordinary temperature until the sodium sulphide has been used up. It is then dilutedwith water. The excess of alkali is neutralized with mineral acid and the reduced dyestufl' is salted out and filtered.

When dry the new dyestufi' which has the probable formula:

' on /b k/ is a black-brown powder which is soluble in water to a violet-brown solution becoming brown-red on addition of acid, blue on addition of sodium carbonate solution and bluish-red on addition of caustic alkali. It dies wool in an acid bath violet or brownishblack shades which become grey or black whenafter-chromed and are very fast.

Example 2.

A freshly made paste of as high a concentration as possible containing 44 parts of the free dyestufi' acid of the dyestufi' made by coupling the nitrated' diazo-compound of 1-a1nino-2 hydroxynaphthalene 4 sulphonic acid with asna'phthol is introduced into a solution of 18.4: parts of sodium sulfhydrate and parts of water, whereupon aslight evolution of sulphuretted hydrogen occurs. The mixture is warmedfor some time at 50 (1. whereby the dyestuff is converted into its a amino-derivative.

The dyestuff is identical with thatv obtained as described in Example 1 and is separated as thereinstated.

".Ewample 3. v

. A suspension as concentrated as possible of the dyestuff made by coupling 4:6.5 parts of B'naphthol with 95 parts of the sodium salt of the nitrated diazo-comp ound of 1 amino2-hydroxynaphthalene l-sulphonic acid, containing about 5 parts of sodium car- ,bonate, is mixed, while stirring, with a lukecomes a thin fluid.

warm solution of 72 parts of crystallized sodium sulphide, 9.6 parts of sulphur, 12 parts of caustic soda and 58 parts of water; the whole isheated for some time at 80-90 (1. with continued 7 stirring, whereby the mass, which is at first a thick magma, be-

The product of reaction is then poured into water, the excess of alkali is neutralized in greater part with mineral acid and the dyestufi' is'salted out. It is a black-brown powder, soluble in water to a violetdorown solution which, on addition of sodium carhonate solution becomes greenish-blue; blueviolet on addition of caustic alkali and redbrown on addition of acid.

The new dyestuif dyes wool in an acid bath red-violet or brownish-black shades, which become grey or black and very fast when after-chromed.

Example 1,.

A suspension as concentrated as possible of the'dyestufi' made by coupling 150 parts of B-naphthol with 285 parts of the sodium salt of the nitrated diazo-compound .of 1-amino-2-hydroxynaphthalene-4t sulphonic acid, is mixed, while stirring with a molten mixture of 50 parts of water and 360 part: of crystallized sodium sulphide. The mass is then heated to'75'8 0 C; with continued stirring, whereby reaction occurs in the course of Whichthe mixture becomes a thin fluid. Stirring is continued for some time at 80 0., then the mixture is diluted with a 7 naphahtlene-4-su1phonic acid in the presence of 145 parts ofcaustic'soda solution of 80 per cent. strength and 1 0 parts of sodium carbonate, is mixed with 360 parts of erystallized sodium sulphide and the mixture is stirred for a sufiiciently longtime, It. is then diluted withwater and the dyest-uti is separated as a brown-black precipitate salting out and slightly acidifying the liquid obtained. U .c

When dry the new dyestuff is a black-- brown powder which dissolves in waterto violet-brown solution becoming Bordeaux red on addition of acid, blue onaddition of sodium carbonate solution and brown-red'on additionof caustic alkali. It dyeswool in anacid bath black-blue shades which become black byafter-chroming. a What we claim is: n y I 1. As anew process the herein described manufacture of new dyestuffs, consisting in treating with a water-soluble sulfide the dyestuffs obtained by coupling the nitrated diazo-compound of lamino-Q-hydroxynaphathalene-4-sulphonic" "acid with a naphthol. 4 y

2. a new process the herein described manufacture ofnew dyestuffs, consisting in treating with a water-soluble sulfide the dyestuffs obtained bycoupling the nitrated diazo-compound of: l-amino-fl-hydroxynaphthalene--sulphonie acid with an unsubstituted naphthol. i i

I 3. As anew process the 'hereindescribed manufacture of new dyestuffs, consisting in treating with an alkali metal sulphide the dyestuffs obtained by coupling thenitrated diazo-compound of Y l-amino-Q-hydrox} naphthalene l-sulphonic acid with an substituted naphthol.

4. As a new process the her-em described manufaoture of new dyestufis, consisting in treating with an alkali metal sulphide. the dyestuffs obtained by coupling thenitrated diazo-compound of 1-amino-2-hydroxynaphahalene-l-sulphonic acid with an anaphthol.

5. As new products the new dyestuffs of the probable general formula:

(in which R indicates an hydroxynaphthalene nucleus which the azo-bridge is attached in an ortho-position to the hydroxylgroup), which dyestuffs are obtained by reduction of the dyestuffs obtained by coupling the nitrated diazo-compound of 1-amino-2-hydroXyna-phthalene 4 suphonic acid with a naphthol, and which dyestuffs form blackish-brown powders which dissolve in a sodium carbonate solution with a blue colour and in dilute caustic soda solution with a blue-red to blue-violet colour, dyeing wool in an acid bath dark brown to black-blue shades which become black by after-chroming and are very fast.

6. As new products the new dyestuffs of the probable general formula:

(in which R indicates an hydroxynaphthalene nucleus which carries no further substituents and to which the azo-bridge is attached in an ortho-position to" the hydrooxyl-group), which dyestuffs are obtained by reduction of the dyestufis obtained by coupling the nitrated diazo-compound of with a blue-red to blue-violet colour, dyeing wool in an acid bath dark brown to black: blue shades which become black by afterchromihg and are very fast.

7. As a new product the new dyestuff of the probable formula:

which dyestufi is obtained by reduction of the dyestufi' obtained by coupling the nitrated diazo-compound of l-amino-2-hydrooxynaphthalene-i-sulphonic acid with anaphthol, and which differs from the parent dyestuffs by its superior solubility, even in calcareous water, its superior levelling, and its fastness to potting, and which dyestufi' forms a black-brown powder which is soluble in water to a violet-brown solution becoming brown-red on addition'of acid, blue on addition of sodium carbonate solution and bluish-red on addition of caustic alkali, dyeing wool in an acid bath violet or brownish-black shades which become grey gr black by after-chroming and are very ast.

8. Material dyed with the dyestuffs according to claim 5.

9. Material dyed with the dyestuffs according to claim 6.

10. Material dyed with the dyestuff according to claim 7.

In witness whereof we have hereunto signed our names this 19th day of March 1924:, in the presence of two subscribing witnesses.

FRITZ STRAUB. HERMANN SCHNEIDER.

Witnesses AMAND BAUER, MADELEINE SPENGLER. 

